Petroleum resin and sizing composition prepared from an unsaturated dicarboxylic acid adduct thereof



United States Patent 3,379,663 PETROLEUM RESIN AND SIZING COMPOSITION PREPARED FROM AN UNSATURATED DICAR- BOXYLIC ACID ADDUCT THEREOF Koji Takei, Iwakuni-shi, Yamaguchi-ken, and Keiichi Miyamoto and Takeji Kenmotsu, Ohtake-shi, Hiroshima-ken, Japan, assignors to Mitsui Petrochemical Industries, Ltd., Tokyo, and Arakawa Rinsan Kagaku Kogyo Kabushiki Kaisha, Osaka, Japan, both corporations of Japan No Drawing. Filed Mar. 31, 1964, Ser. No. 356,046 Claims priority, application Japan, Apr. 2, 1963, 38/ 16,260 2 Claims. (Cl. 26023.7)

The present invention relates to a process for the manufacture of hydrocarbon resins using hydrocarbon as a raw material and sizing agents for paper in which the obtained hydrocarbon resins are used.

The hydrocarbon resins have been generally used as a raw material for floor material, road pavement, paint, rubber compounding agent, adhesive, molded laminate, etc. Furthermore, rosins have been normally used as a main ingredient for the sizing agent for paper making, but recently it has been proposed that a hydrocarbon resin be used as the sizing agent for paper making in place of rosin. Various investigations for using hydrocarbon resin for sizing agent have been made. For example, it has been known to manufacture a paper sizing agent using the hydrocarbon resin by adding and treating hydrocarbon resin with unsaturated acid and/or rosin. As one of the raw materials for hydrocarbon resin, it is proposed that unsaturated hydrocarbon in a fraction which is obtained in a cracking and reforming of petroleum, has a boiling point of more than 130 C. and is aromatics-rich is used. However, the sizing efliciency of the hydrocarbon resin which is used with such aromatics-rich fraction as the raw material is not often reached to the sizing efiiciency simi- I lar to that of fortified rosin sizing agent depending upon paper making conditions, even if the hydrocarbon resin is modified by adding rosin, unsaturated acid, etc. thereto. Particularly, the sizing efficiency is bad when the temperature of paper making is low.

These points are very serious because the speed of paper making machines is' increasing and the drying step is becoming shorter. The added amount of sizing agent is increased in order to obtain hard size, a coagulation of resin occurs and the felt and wire of paper making machine are contaminated.

As explained above, the use of hydrocarbon resin as a paper sizing agent is still unsatisfactory.

As a result of various investigations of these points, we have now found a process for the manufacture of hydrocarbon resin which is industrially useful by effectively utilizing unsaturated hydrocarbon in a hydrocarbon fraction which is aromatics-rich.

Therefore, the first object of the present invention is to provide a process for the manufacture of hydrocarbon resins capable of being used as a sizing agent for paper and paper board having an excellent efiiciency.

The second object of the present invention is to provide the said hydrocarbon resins with a sizing efficiency of which is not decreased even if a lower surface temperature of the paper in a paper making machine, such as 80 C., is used for the drying and which can provide a excellent sizing agent having no objection even when a larger amount of it is added to make a hard sized paper.

A further object of the present invention is to provide a process for the manufacture of the sizing agent.

These and other objects of the present invention will be apparent from the following descriptions.

According to the present invention, there is provided a 3,379,663 Patented Apr. 23, 1968 process for the manufacture of hydrocarbon resins characterized in that aromatic rich hydrocarbons having a boiling point of more than C. which were obtained as by-product from cracking or reforming processes of petroleum are incorporated with such low-boiling hydrocarbons at least a part of which consists of one or more unsaturated hydrocarbons as having a boiling point in the range of 15 C. to 45 0., preferably -15 C. to 15 C. and the resultant mixture is polymerized.

Generally, heavy petroleum fraction such as light naphtha, heavy naphtha, gas oil, etc. may be cracked in a short time and under a comparatively low pressure in presence of steam at a temperature of 500 to 900 C. Hydrocarbons derived from such a steam cracking process usually consist of a considerably large amount of diolefin, olefin, aromatic hydrocarbon and some paraffin.

A fraction containing hydrocarbons having carbon atoms of more than 8 from which a fraction containing hydrocarbons having atoms of 1 to 7 is removed by a continuous fractional distillation containing a large amount of unsaturated hydrocarbon, for example a fraction having a boiling point of 130 to 300 C. has nearly the following composition:

Percent by weight Styrene, indene and their derivatives 30-60 Olefins 5-10 Aromatics 20-40 Paraifins and naphthenes 10-20 Diolefins 0-5 Although it is possible to change a softening point and bromine value of the formed hydrocarbon resin and also a ratio of aromatics to aliphatic hydrocarbons in the hydrocarbon resin by changing the adding amount of the low-boiling hydrocarbon fraction having less than 7 carbon atoms to the above mentioned hydrocarbons, we have found that when certain low boiling hydrocarbon, namely unsaturated hydrocarbon or fraction containing it which has a boiling point in a range of 15 to 45 C., preferably -15 to 15 C. is used, it is possible to manufacture hydrocarbon resin which is very suitable for use as a raw material for paper sizing agent.

As is clear from the comparative data shown in Examples 8 and 10 hereinafter referred to namely, if low boiling hydrocarbons having a boiling point in the range other than that of the present invention are used as the added component, the obtained results are considerably inferior to those obtained by using hydrocarbon resin manufactured by the process of the present invention in paper sizing efficiency and therefore a satisfactory result cannot be obtained.

As the low boiling hydrocarbons to be used as the added component in the process of the present invention, it is possible to use unsaturated hydrocarbons having carbon atoms of 4 to 5 such as butene, butadiene, pentene and pentadiene which are obtained as by-product from the cracking or the reforming of petroleum and have a boiling point in range of -15 to 45 C., but the preferable one is hydrocarbon containing mainly 4 carbon atoms which has a boiling point in range of l5 to 15C. and contains olefins and diolefins such as butene and butadiene.

The composition of the preferable one is for example unsaturated hydrocarbon-rich fraction having the following composition:

Percent by weight Olefins 40-70 Diolefins 20-60 Parafiins 10-30 The most suitable added amount of this low boiling fraction may vary depending upon various properties of the hydrocarbons boiling above 130 C. such as boiling range, the degree of unsaturation and content of aromatic hydrocarbon as well as various properties such as boiling range and contents of olefin and diolefin of low boiling fraction to be added, but when each fraction which is shown in the after-mentioned examples is used it is normal to use less than 200 parts by weight of the low boiling fraction per 100 parts by weight of high boiling fraction. In this case, for example, it is preferable to change the polymerization conditions with the increase or the decrease of the added amount, because the polymerization conditions in which hydrocarbon resin for paper sizing agent gives a preferable sizing efiiciency is not same.

The polymerization in the process of the present invention can be carried out by various methods such as radical and ionic polymerization, but most normal method is one in which cationic type polymerization catalyst such as aluminium trichlo-ride, aluminium tribromide, boron trifluoride, titanium tetrachloride, ferric chloride is used. These catalysts can be used in solid, liquid or gaseous states, but it is convenient to use them in form of liquid. Although the amount of these catalyst may be varied, it is practical to use these catalyst in an amount of 0.5 to 3.0% by weight of the raw material unsaturated hydrocarbon.

The polymerization temperature may be varied in a wide range, but the preferable temperature is -80 to 80 C. In order to carry out the polymerization at a high emperature, it is necessary to use a polymerization vessel which is pressure resist-ant.

The polymerization time, in case of a batch type, is preferable 0.5 to 10 hours, but a suitable time is normally l to 5 hours.

The addition of the low boiling fraction to the high boiling fraction may be carried out before, after or when the catalyst is added to the high boiling fraction, or the low boiling fraction to which a part of the catalyst was already added may be added to the high boiling fraction, but in any case a hydrocarbon resin which has a superior sizing property can be obtained by suitable regulating the polymerization time and the amount of catalyst.

The reaction liquid in which the polymerization was completed is generally added with an aqueous alkali or an alcoholic alkali to decompose and deactivate the catalyst and then the reaction product treated with alkali is washed with water or water containing a little quantity of alcohol. At that time the reaction product liquid is heated to remove unreacted low boiling fraction in the form of gas from the former. The pale yellow transparent liquid is obtained. The reaction liquid which is obtained as a pale yellow transparent liquid is stripped under a reduced pressure to obtain the product hydrocarbon resin as a residue.

The polymerization process according to the present invention can be carried out by a batch type and continuous type can also be used. The hydrocarbon resins which are obtained by these polymerization method is satisfactorily used for a sizing agent.

The present invention is illustrated but not limited by the following examples and comparative examples in which the parts and percentages are by weight.

Example 1 100 parts of a hydrocarbon fraction which were obtained in a steam cracking of petroleum, had a boiling point of 130 to 240 C. and contained 52% of styrene, indene and their derivatives, 39% of other aromatics, 3% of olefin, less than 1% of diolefin and 5% of parafiin and naphthene were added with 20 parts of a hydrocarbon fraction which had a boiling point of l to 15 C. and contained 34% of olefine; 42% of diolefin and 24% of paraffin. To the mixture was added 1% of boron trifluoride-phenol complex as catalyst and the mixture was then polymerized at the temperature of 30 C. for 3 hours.

The reaction liquid was added with 10% of 10% aqueous sodium hydroxide solution and then was heated at the temperature of 80 C. and an atmospheric pressure. At that time, 6 parts of unreacted low boiling fraction were removed as a gas.

The reaction product was washed with a hot water of 50 C. in 3 times and thereafter was heated to 180 C. under a reduced pressure of mm. mercury to remove a unreacted matter and low polymers. As a result, 54 parts of a pale yellow hydrocarbon resin were obtained.

Example 2 The procedure described in Example 1 was repeated except that 10 parts of a hydrocarbon fraction which had a boiling point of l0 to 0 C. and contained 31% of olefin, 54% of diolefin and of parafiin were used, 52 parts of hydrocarbon resin were obtained. In this case, 2.5 parts of gas were removed.

EXample 3 The procedure described in Example 1 was repeated except that parts of a hydrocarbon fraction which had a boiling point of l5 to 10 C. and contained 28% of olefin, 42% of diolefin and 30% of paraffin were used. 59 parts of hydrocarbon resin were obtained. In this case, 14 parts of gas were removed.

Example 4 100 parts of high boiling hydrocarbon described in Example 1 were added with 100 parts of low boiling hydrocarbon described in Example 3. The mixture was added with 1% of boron trifiuoride-ethylether complex as a catalyst, and were polymerized at the temperature of C. for 5 hours. The polymerization liquid was added with 10% sodium hydroxide methanolic solution in the amount of 10% based upon the raw hydrocarbon mixture.

The mixture was agitated was then raised to a room temperature was thereafter added with 10% of water and then was heated to the temperature of C. Further operation was carried out as described in Example 1. 81 parts of hydrocarbon resin was obtained. In this case, 35 parts of gas were removed.

Example 5 parts of the high boiling hydrocarbon oil as described in Example 1 were added with 30 parts of hydrocarbon containing 58% of olefin and 42% of parafifin which was obtained by removing diolefin from a hydrocarbon fraction boiling in 10 to 15 C. as used in Example I. By the same operation as described in Example 1, 48 parts of the high boiling hydrocarbon resin were obtained. In this case, 18 parts of gas were removed.

Example 6 100 parts of hydrocarbon fraction oil as described in Example 1 were added with 30 parts of hydrocarbon fraction which had a boiling point of -l5 to 45 C. and contained 52% of olefin, 30% of diolefin and 18% of parafiin. By the same operation as described in Example 1, 52 parts of hydrocarbon resin were obtained. In this case, 6.5 parts of gas were removed.

Example 7 100 parts of the high boiling hydrocarbon fraction oil as described in Example 1 were added with 20 parts of hydrocarbon fraction which had a boiling point of 0 to 45 C. and contained 48% of olefin, 32% of diolefin and 20% of parafiin. By the same operation as described in Example 1, 54 parts of hydrocarbon resin were obtained. In this case 7 parts of gas were removed.

Comparative Example 1 Example 1 was repeated except that low boiling hydrocarbon fraction was not used. Thus, 44 parts of hydrocarbon resin were obtained.

Comparative Example 2 100 parts of the high boiling hydrocarbon fraction oil as described in Example 1 were added with parts of hydrocarbon fraction which had a boiling point of 60 to 100 C. and contained 31% of olefin, 8% of diolefin, 18% of paraflin and 43% of aromatics. By the same operation as described in Example 1, parts of hydrocarbon resin were obtained.

Comparative Example 3 resin of the present invention cannot be ascertained by a simple supposition, it can be completed only by repeating investigation of various hydrocarbon resins and vari ous dispersing or solubilizing processes with a consideration for the very delicate function of paper sizing.

The characteristics which are obtained by the process for the manufacture of the sizing agent of the present invention are as follows:

1) Since the addition reactivity of the novel hydrocaron resin with a,,8-unsaturated aliphatic acids or acid anhydrides is larger than the resin which is obtained from only high boiling fraction containing large amount of aromatic hydrocarbon of boiling point of more than 130 C., the procedure is very easy and the loss of the acid component is very small.

(2) A hydrocarbon resin which have a higher reactivity for the above acid component can be obtained by using the raw materials other than the fraction used in the present invention. But although the reactivity for the acid component of the known resins is same as the novel TABLE L-FROPERTIES OF HYDROOARBON RESINS OBTAINED IN ABOVE EXAMPLES AND COMPARATIVE EXAMPLES Examples Comparative exampies Softening point C.) 70 75 67 69 72 81 73 olor 2 12 12 12 10 12 12 11 12 14 12 Bromine value" 51. 2 45. 0 58. 0 82. 8 37. 2 50. 5 59. 4 32. 0 44. 5 52. 2 Acid value O. 3 0. 2 0. 1 0. l 0. 1 0. 2 0. 2 0. 1 0. 1 0. 6 Saponifioation value..- 2. 3 1. 7 2. 2 1. 9 2.0 1.9 2.0 1. 9 2. 8 3. 3 Mean molecular weight 620 650 600 900 620 680 690 730 590 690 1 The softening point was measured by a ball and ring method.

Even if the hydrocarbon resins of the present invention are used by themselves as a sizing agent for paper and paper board by applying them a conventional emulsifying method, they give a superior efficiency to the emulsion of hydrocarbon resin which raw material is a fraction containing large amount of aromatichydrocarbons having a boiling point of more than 130 C.

2 The color was represented by Gardner number.

resin of the present invention, a considerable difference is observed when these addition products are dispersed or solubilized into water, the latter is more dispersible or soluble than the former and the grain size of the latter is finer than that of the former and the dispersion or solution of the latter is more stable than that of the former. The examples are shown in Table 2.

TABLE 2 Meleic Ratio of v Resin Anhydride Rosin Reacted N0. Kind of resin used Amount Amount Amount maleic (g') (g.) (g.) Anhydride (percent) 1 Example I 100 5 10 72 2. Comparative example 3. 100 5 10 71 3 100 7. 5 30 68 4 100 7. 5 30 68 5... 100 10 30 65 6 Comparative example 3 100 10 30 4 However, the characteristic of the present invention is considerable exhibited by incorporating the hydrocarbon resin which is obtained in the process of present invention with a,B-unsaturated aliphatic acids or acid anhydride, and then by adding and mixing with at least one compound (hereinafter refer to rosin and the like) selected from the group consisting of rosins, higher fatty acids and their a,,8-unsaturated aliphatic acids or acid anhydrides partially adducts and thereafter by dispersing or solubilizing into water while the mixture is saponified with alkali. In other word, this novel hydrocarbon resin is especially suitable for the application of the abovementioned dispersing or solubilizing, it gives very easily a stable dispersion or solution, and also the sizing efiiciency is very higher than that of paper sizing agents which are used with any prior hydrocarbon resins, and is not changed by the variation of paper making conditions.

Although a process wherein prior hydrocarbon resins are partially addition-reacted with cap-unsaturated aliphatic acids or acid anhydrolides, rosin and the like to give a paper sizing agent is already known, the present invention is characterized in that such prior art is improved and the particular hydrocarbon resin according to the present invention is very suitably used for such process for the manufacture of sizing agent.

The fact that such process for the manufacture of sizing agent can be very effectively used for the hydrocarbon No. Appearance 1 Brown, lightly turbid solution. 2 Yeilow, opaque emulsion. 3 Brown, substantially transparent solution. 4- Brown, lightly turbid solution. 5 Brown, transparent solution. 6 Brown, slightly turbid solution.

From the above, it is seen that there is dilference between the resin of Example 1 and the resin of Comparative Example 3 lies in their ability to disperse in water of the treated resin, notwithstanding that bromine value and ratio of reacted maleic anhydride are same.

(3) In addition to the fact that the hydrocarbon resin of the present invention gives a considerable sizing efiiciency by reacting it with nip-unsaturated aliphatic acids or acid anhydride to form a partically addition-reacted product, the sizing efiiciency is not influenced even if the amount of the acids is increased. On the contrary, the stability of dispersion and the transparency of the prior hydrocarbon resin are increased when the addition amount of acid to the resin is increased more than but the sizing eficiency is rather decreased.

As mentioned above, this novel hydrocarbon resins have a property which is suitable for applying water dispersing or solubilizing process wherein the novel resins are reacted with o h-unsaturated aliphatic acids or acid anhydride to form a partially addition-reacted resin and the resulting resin and then the mixture is mixed and heated with rosin and the like and thereafter is saponified with alkali. Thus it is possible to obtain a very useful sizing agent by the combination of these two arts, i.e. the manufacturing arts of the hydrocarbon resin and the sizing agent using the resin according to the present invention.

Suitable acidic compounds containing the group include a d-unsaturated aliphatic acids or acid anhydrides, such as acrylic, methacrylic, crotonic, maleic, fumaric, itaconic and citraconic acids and their acid anhydrides. Further citric acid and the like may be mentioned as a compound producing ,fi-Ui'lSfitlll'EltCd polybasic acid by heating. Among them, as monobasic acid has the property which can be polymerized itself by a heating, it is convenient to use dibasic acid.

The rosin and the like which are used in the present invention can give an effect for the dispersing into water of hydrocarbon resin which is added and reacted with n p-unsaturated aliphatic acids. The employing amount of it is sufiicient to use in a small amount because the dispersing into water of the resin is very easy. Namely, it is sufiicient to use it in an amount necessary for a dispersing agent and therefore the necessary amount of it is smaller than in the case that sizing agent is manufactured from the prior hydrocarbon resin. As the examples of above rosins and higher fatty acids, there are mentioned gum rosin, wood rosin, tall oil rosin, FF rosin, tall oil, soybean oil fatty acid, linseed oil fatty acid, coconut oil fatty acid, stearic acid, oleic acid, linoleic acid, etc. The function and effect of these compounds are almost equal and good siZ- ing agent may be obtained. Although suitable employing amount is as shown in the hereinafter mentioned examples, the suitable amount should be selected according to the addition-reaction amount of a,[3-unsaturated aliphatic acids or acid anhydrides for hydrocarbon resins or above rosins or higher fatty acids. Of course, it is also possible to use these acids in combination as a dispersing agent.

The operation conditions in the dispersing or solubilizing process have not serious difficulties because alkali salt of the present hydrocarbon resin containing carboxylic group, rosin and the like is very good dispersibility into water. It is sufficient to treat the above resin mixture together with suitable aqueous alkali solution in a saponifying vessel or emusifying equipment having a conventional agitator and then to dilute the treated matter with water to a desired concentration. As the alkali, it is possible to use hydroxide and/or carbonate of alkali metal, ammonium hydroxide, organic amines, etc.

A process for sizing various paper and paper boards with the sizing agent of the present invention is not different from the prior rosin sizing process and therefore the process can be carried out in any paper machine without a trouble. As carried out generally, namely, the

necessary amount of the sizing agent is added into a pulp suspension of which a beating was completed and uniformly mixed together, and then added with alum, and

the pulp suspension is made acidic and is sheeted on a wire and thereafter the sheet is dried.

As concretely explained above, when the hydrocarbon resin of the present invention is used as a sizing agent for paper making, an influence for sizing efiiciency of drying temperature at the paper making is almost negligible and the excellent sizing efiiciency can be obtained by the use of small amount of u,B-unsaturated acid and rosin. Therefore, the present sizing agent is technically and economically superior than the prior sizing agent.

The hydrocarbon resins obtained by the process of the present invention is of use not only as a sizing agent but also a raw material for floor material, road pavement, paint, rubber compounding material, adhesive, molded laminate, etc.

The embodiments'of paper making using the hydrocarbon resin according to the present invention as a sizing agent are illustrated by the following examples.

Example 8 Ten kinds of hydrocarbon resins which were obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were treated as follows, respectively:

kg. of hydrocarbon resin and 5 kg. of maleic anhydride were charged in a closed type stainless steel reactor which was provided with an agitator, a thermometer and a condenser and had a capacity of 200 liters and heated to melt them. After the reaction temperature was reached to 200 C., agitation was continued at that temperature for 6 hours. The cover of reactor was then opened and the reactor was quickly charged with 10 kg. of tall oil rosin and the cover of the reactor was closed and then an agitation was again continued at the temperature of 200 C. for 2 hours. After the completion of reaction, the content was run out from the reactor while the fluidity of the contents was maintained to give a brown transparent solid resin. All ten kinds of treated resins thus obtained had a saponification value of 60 to 63, respectively and their softening points were raised to 5 to 10 C. more than the original hydrocarbon resins.

100 kg. of the treated hydrocarbon resin thus obtained and 30 kg. of aqueous alkali solution containing 6 kg. of caustic potash were charged in a closed type iron reactor which was provided with a strong agitator, thermometer, condenser and pouring inlet of water and had a capacity of 300 liters and the mixture was heated while agitating to 100 C. and the resin was gradually attacked with alkali to give an uniform liquid. The heating was stopped and the content was poured with about 200 kg. of hot water of 60 C. with agitation to give a dispersion containing 30% of resin and after cooling the dispersion was withdrawn. The dispersions which were obtained by using the resins of Examples 1 to 7 were all a brown and lightly turbid solution, but the dispersions which were obtained by using the resins of Comparative Examples 1 to 3 were yellow opaque emulsion.

30% aqueous dispersions thus obtained were diluted with water until the amount of resin was reached to 5% to give a sizing solution, respectively.

A given amount of above various sizing solutions were added with a given amount of bleached sulfite pulp suspension containing 1% of dry pulp which was beated to the freeness 420 ml. After an agitation Was carried out until the sizing agent was uniformly mixed, 5% based on the weight of dry pulp of aluminium sulfate in the form of aqueous solution was added and then well agitated. The stock comprising these sizing pulp was sheeted in TAPPI standard sheet machine to a basis weight of 56 to 57 g./m. On the obtained paper, the sizing degree (that is seconds required for the permeation of reagent) was measured by the Stockigt method. In that period the temperature of the water was 20 C The sizing degree which was obtained on each sample are shown in Table 3.

Amount of sizing agent added (resin amount/dry pulp by weight) 0.5% by weight 1.0% by weight 0.5% by weight 1.0% by weight Sizing degree (sea):

Example 1 27.2 33.1 28. 4 33. 3

Example 2. 25.0 29.6 26 1 30.9

Example 3 26.5 34.2 23. 1 32.6

Example 4.- 28.8 34. 4 29.6 36. 5

Example 5 24. 7 29.4 23. 33. 3

Example 3 23. 2 2s. 26.6 31. 4

Example 7. 23. 8 27.1 25. 2 32. 1

Comparative example 1 7. 2 18. 7 17. 6 29. 6

Comparative example 2.- 12. 6 22.3 20.1 27. 8

Comparative example 3 17.0 24. 9 22. 7 29.1

Example 9 The composition of tall oil used were as follows:

100 kg. of each hydrocarbon resin in Example 1 and Percent Comparative Example 1 were incorporated with 10 kg. 45 of maleic anhydride, respectively. The mixture was addi- 2O QIeICaCId 23 tion reacted in the reactor and under the same reaction Llnohc acld 18 conditions as described in Example 8 and then was other fafty aclds 7 added with 50 kg. of gum rosin by a similar operation. Unsaponlfied matters 7 Thus, a transparent brown solid resin was obtained. The s'aponification value and softening point of the obtained resins were 113 and 79 C. in the resin of Example 1 and 113.5 and 81 C. in the resin of comparative TABLE 5.COMPARISON BETWEEN SIZING DEGREE Drying Conditions of Sheet 80 C., 5 mins. 110 0., 5 mins.

The sizing efficiency of each sizing agent was measured by the same conditions as described in Example 8 and the results are shown in Table 5.

Amount of sizing agent added (resin amount/dry pulp by weight)- 0.5% by weight 1.0% by weight 0.5% by weight 1.0% by weight Sizing degree (sec Example 1 25.4 31.8 26.1 31. 2 Example 4 23.1 33. 9 27.6 33. 7 Comparative Example 1-... 6.5 15. 2 13. 8 25. 6 Comparative Example 2 16. 2 21. 5 21. 6 26. 7

example, respectively. 100 kg. of each obtained resin were charged in the same reactor as described in Ex- What we claim is: ample 8 and were added with kg. of aqueous alkali 40 1. A process for the manufacture of hydrocarbon solution containing 11 kg. of caustic potash. Further resins having a bromine value in a range of 37.2 to 82.8 treatment was carried out as described in Example 8 to and a softening point in a range of 55 C. to 75 C. obtain a sizing solution which was a brown transparent which comprises incorporating a low-boiling hydrocarsolution containing 5% of resin. bon fraction boiling in a range of 15 C. to 15 C.

The sizing agents which were obtained by applying the which is aliphatic unsaturated hydrocarbon-rich in an process of Examples 8 and 9 to the hydrocarbon resins aromatic-rich hydrocarbon fraction boiling in a range of of Example 1 and Comparative Example 1 refer to 130 C. to 300 C. which was obtained as lay-product 1-8, Cl- 8, 1-9 and Cl-9, respectively. The from the cracking or reforming of petroleum in an sizing efficiency of l-8, CL-8, 1-9 and Cl-9 amount of 0.1 to 1 part by Weight of the low-boiling are shown in Table 4. The measuring conditions are the fraction per part by weight of the high-boiling fraction same as described in Example 8. and polymerizing the mixture thus obtained at a tem- TABLE 4.OOMPARISON BETWEEN SIZING DEGREE Drying Conditions of Sheet 80 C., 5 mins. 110 0., 5 mins.

Amount of sizing agent added (resin amount/dry pulp by weight)- 0.5% by weight 1.0% by Weight 0.5% by weight 1.0% by weight Sizirlig degree (see):

Example 10 perature of 80 C. to 80 C. in the presence of a cationic type polymerization catalyst.

2. A sizing agent for making paper and paper board consisting essentially of an aqueous dispersed or solu- 5 bilized product which was obtained by reacting 100' parts by weight of a hydrocarbon resin with 5 to 10 parts by weight of a compound selected from the group consisting of an alpha,beta-unsaturated aliphatic dicarboxylic acid Four kinds of hydrocarbon resins which were obtained in Examples 1 and 4 as well as Comparative Examples 1 and 2 were treated by applying the operation and condition as described in Example 8, using itaconic acid, tall oil and triethanol amine. The incorporating ratios of materials and properties of treated resins were as follows and acid 'anhydride thereof to form a partial addition Hydrocarbon resin kg 100 reaction product thereof, mixing (1) the product thus Itaconic acid kg 5 obtined With (2) 10 to 50 parts by weight, based on 100 Tall oil kg- 25 parts by weight of the hydrocarbon resin used, of at Saponi-fication value of treated resin 66.2 least a member selected from the group consisting of Softening point of treated resin C 67 rosins, higher fatty acids, -alpha,beta-unsaturated aliphatic Triethanol amine kg 11.2 dicarboxylic acid partial adducts of rosins, alpha,beta- 1 1 unsaturated aliphatic dicarboxylic acid anhydride partial adducts of rosins, alpha,beta-unsaturated aliphatic dicarboxylic acid partial adducts of fatty acids and alpha,betaunsaturated aliphatic dicarboxylic acid anhydride partial adducts of fatty acids and saponifying the mixture thus obtained with an aqueous alkali to disperse or solubilize it into Water, the hydrocarbon resin being prepared by incorporating (a) a low-boiling hydrocarbon fraction boiling in a range of 15 C. to 15 C. which is aliphatic unsaturated hydrocarbon-rich into (b) an aromaticrich hydrocarbon fraction boiling in a range of 130 C. to 300' C. which was obtained as by-product from the cracking or reforming of petroleum, in an amount of 0.1 to 1 part by Weight of the low-boiling fraction per part by Weight of the high-boiling fraction, polymerizing the mixture thus obtained at a temperature of 80 C. to 80 C. in the presence of a cationic type polymerization catalyst to form the hydrocarbon resin having a bromine value in a range of 37.2 to 82.8 and a softening point in a range of 55 C. to 75 C.

References Cited UNITED STATES PATENTS 3,279,975 10/1966 Yoshii et a1. 260-27 3,287,332 11/1966 Saeki et a1. 260-82 2,946,775 7/1960 De Vries et al. 260-82 2,991,275 7/1961 Fefer 260-82 2,994,689 8/1961 Banes et a1. 260-82 3,005,800 10/1961 Powers et a1. 260-82 3,161,620 12/1964 Perkins et al. 260-23 3,193,449 7/1965 Aldrich et a1. 260-27 3,211,683 10/1965 Arakawa et a1. 260-27 DONALD E. CZAJA, Primary Examiner.

R. A. WHITE, Assistant Examiner. 

2. A SIZING AGENT FOR MAKING PAPER AND PAPER BOARD CONSISTING ESSENTIALLY OF AN AQUEOUS DISPERSED OR SOLUBILIZED PRODUCT WHICH WAS OBTAINED BY REACTING 100 PARTS BY WEIGHT OF A HYDROCARBON RESIN WITH 5 TO 10 PARTS BY WEIGHT OF A COMPUND SELECTED FROM THE GROUP CONSISTING OF AN ALPHA,BETA-UNSATURATED ALIPHATIC DICARBOXYLIC ACID AND ACID ANHYDRIDE THEREOF TO FORM A PARTIAL ADDITION REACTION PRODUCT THEREOF, MIXING (1) THE PRODUCT THUS OBTAINED WITH (2) 10 TO 50 PARTS BY WEIGHT, BASED ON 100 PARTS BY WEIGHT OF THE HYDROCARBON RESIN USED, OF AT LEAST A MEMBER SELECTED FROM THE GROUP CONSISTING OF ROSINS, HIGHER FATTY ACIDS, ALPHA,BETA-UNSATURATED ALIPHATIC DICARBOXYLIC ACID PARTIAL ADDUCTS OF ROSINS, ALPHA,BETAUNSATURATED ALIPHATIC DICARBOXYLIC ACID ANHYDRIDE PARTIAL ADDUCTS OF ROSINS, ALPHA,BETA-UNSATURATED ALIPHATIC DICARBOXYLIC ACID PARTIAL ADDUCTS OF FATTY ACIDS AND ALPAH,BETAUNSATURATED ALIPHATIC DICARBOXYLIC ACID ANHYDRIDE PARTIAL ADDUCTS OF FATTY ACIDS AND SAPONIFYING THE MIXTURE THUS OBTAINED WITH AN AQUEOUS ALKALI TO DISPERSE OR SOLUBILIZE IT INTO WATER, THE HYDROCARBON RESIN BEING PREPARED BY INCORPORATING (A) A LOW-BOILING HYDROCARBON FRACTION BOILING IN A RANGE OF -15*C. TO 15*C. WHICH IS ALIPHATIC UNSATURATED HYDROCARBON-RICH INTO (B) AN AROMATICRICH HYDROCARBON FRACTION BOILING IN A RANGE OF 130*C. TO 300*C. WHICH WAS OBTAINED AS BY-PRODUCT FROM THE CRACKING OR REFORMING OF PETROLEUM, IN AN AMOUNT OF 0.1 TO 1 PART BY WEIGHT OF THE LOW-BOILING FRACTION PER PART BY WEIGHT OF THE HIGH-BOILING FRACTION, POLYMERIZING THE MIXTURE THUS OBTAINED AT A TEMPERATURE OF -80*C. TO 80*C. IN THE PRESENCE OF A CATIONIC TYPE POLYMERIZATION CATALYST TO FORM THE HYDROCARBON RESIN HAVING A BROMINE VALUE IN A RANGE OF 37.2 TO 82.8 AND A SOFTENING POINT IN A RANGE OF 55*C. TO 75*C. 